CN101177748A - Method for manufacturing difficult-to-form pure rhenium sheet - Google Patents
Method for manufacturing difficult-to-form pure rhenium sheet Download PDFInfo
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- CN101177748A CN101177748A CNA2007101792629A CN200710179262A CN101177748A CN 101177748 A CN101177748 A CN 101177748A CN A2007101792629 A CNA2007101792629 A CN A2007101792629A CN 200710179262 A CN200710179262 A CN 200710179262A CN 101177748 A CN101177748 A CN 101177748A
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Abstract
The invention pertains to the powder metallurgical preparation field, which more particularly relates to a manufacturing method of difficult deformation pure rhenium plate. The method comprises preprocessed high pure ammonium rhenate and elaborately selected molding and sintering high pure rhenium powder obtained through second phase reduction. An open type stamper guarantees thin rhenium plate materials with Poisson ratio reaches up to 16 can be pressed. The density of the rhenium plate can reach 95 percent of the theory density thorough high-temperature sintering; by strictly controlling amount of deformation per pass, cold rolling and intermediate annealing process are adopted, and the rhenium plate can be rolled with theory density more than 99 percent, thickness 0.4mm, dimension 320 multiplied by 320mm. Compared with the prior art, the invention has the advantages of eliminating work hardening phenomenon and manufacturing finished rhenium plates with different dimensions according to requirements.
Description
Technical field
The invention belongs to field of powder metallurgy preparation, particularly a kind of manufacture method of difficult-to-form pure rhenium sheet.
Background technology
Rhenium metal has high abrasion, solidity to corrosion, high conduction characteristic and can keep high intensity and good creep-resistant property and good thermoelectricity capability under high temperature and temperature shock situation, in electronic engineering, be commonly used for the emtting cathode filament, picture tube filament, extraordinary lamp filament, X-ray target, pyrostat, all many-sides such as nuclear power.Particularly rhenium metal has played irreplaceable effect in the semi-conductor chip production of high speed development.
But because the work hardening speed of rhenium metal is very fast, it is very difficult to cause it to process particularly deep processing.Adopt the heat processing technique of common refractory metal to be not suitable for rhenium, form the fragility phase, can't realize hot-work because the oxide compound of rhenium distributes along crystal boundary.So far, relevant hot worked technique means at rhenium still is in conceptual phase, and adopts cold processing technique that system's report was not arranged as yet yet.
Summary of the invention
The object of the present invention is to provide a kind of work hardening phenomenon of eliminating rhenium metal, can produce the manufacture method of the difficult-to-form pure rhenium sheet of different size according to demand.
According to above-mentioned purpose, the principle of work of technical solution of the present invention is:
The present invention adopts powder metallurgy technology to produce suitable rhenium sheet material, and further the smooth implementation cold processing technique is aided with thermal treatment process simultaneously and successfully produces the qualified rhenium sheet of different size.Utilizing the powder metallurgy principle to make difficult distortion rhenium sheet is basis of the present invention, and it is directly connected to the formability of pressed compact, sintering character and processing characteristics.
Powder preparation technique among the present invention is at first high-purity rehenic acid crystalline ammonium particle promptly to be crushed to certain particle (100～-300 order) through pre-treatment; In hydrogen, carry out low-temperature reduction (controlled temperature is at 230～350 ℃) then, and reduzate handled again, promptly broken (mistake-100～-150 mesh sieves) then carried out sufficient secondary reduction (controlling reduction temperature at 800～950 ℃) and obtained low oxygen content less than 0.1% pure rhenium powder in hydrogen.
Because the work hardening speed of pure rhenium powder is very fast, is difficult for press forming, moreover because the Poisson's Ratio value of pressed compact (long width/) very big (greater than 16), the pressed compact during demoulding is because elastic after effect is easily broken.Therefore, the present invention has adopted and added proper amount of lubricating agent (as paraffin) in powder, can reduce the mutual frictional force of powder and pressing mold, and the intensity that improves pressed compact reaches the purpose of shaping.
Carry out high temperature sintering after pressed compact process dewaxing treatment and the pre-burning under hydrogen shield, sintering temperature is controlled at 2000～2340 ℃, reaches more than 95% of theoretical density until density, and thickness is 4～12mm, the sintering blank that crystallization is even, fine and closely woven.
Usually refractory metal (as tungsten, molybdenum) all is to process under the high temperature about 1500 ℃, but because rhenium is processed easy oxidation under high temperature unprotect atmosphere, and oxide compound produces fragility along the crystal boundary distribution, can not realize hot-work.What therefore the present invention adopted is cold rolling processing at normal temperatures, and strict control pass deformation (8～15%).Because the speed of the work hardening of rhenium is very fast, even a time distortion back hardness doubles rapidly, therefore adopt every time distortion back in hydrogen, to carry out The high temperature anneal (1500～1800 ℃ of annealing temperatures, annealing time is 30～120min), make it eliminate work hardening phenomenon and crystallization control is evenly fine and closely woven, then descend a time rolling.Circulation is processed like this, thermal treatment is until reaching desired size, and last annealed processing obtains finished product rhenium sheet.
According to above-mentioned purpose and principle of work, the concrete technical scheme of the present invention comprises following concrete steps:
A, powder process and reduction:
At first with high-purity rehenic acid crystalline ammonium particle through pre-treatment, be crushed to-100～-300 orders; In hydrogen, carry out low-temperature reduction then, control reduction temperature, and reduzate is handled grinding broken mistake-100～-150 mesh sieves again at 230～350 ℃; Then in hydrogen, carry out sufficient secondary reduction, control reduction temperature at 800～950 ℃, obtain oxygen level less than 0.1% and granularity be 2～6 μ m, the pure rhenium powder of purity＞99.95%;
B, pressed compact:
Adopt removable mold (open pressing mold) to be pressed; Be aided with the lubricant that adds 1.5～3% (mass percents) in powder simultaneously, making thickness is 5～15mm, and the Poisson's Ratio value is greater than 16 pressed compact;
C, sintering warpage:
Carry out high temperature sintering after pressed compact process dewaxing treatment and the pre-burning under hydrogen shield, sintering temperature is controlled at 2000～2340 ℃, reaches more than 95% of theoretical density until density, and thickness is 4～12mm, the sintering blank that crystallization is even, fine and closely woven;
D, rolling deformation:
What adopt is cold rolling processing at normal temperatures, and strict control pass deformation 8～15%; Adopt every time distortion back in hydrogen, to carry out The high temperature anneal, 1500～1800 ℃ of annealing temperatures, make it eliminate work hardening phenomenon and crystallization control is evenly fine and closely woven, then descend a time rolling, circulate like this process, thermal treatment is until reaching desired size; Last annealed processing, annealing temperature are 1500～1800 ℃, and annealing time is 30～120min, obtain finished product rhenium sheet.
With lubricator be a kind of in paraffin or the glycide in the aforesaid method.
The present invention compared with prior art has the work hardening of elimination phenomenon, can produce the advantage of different size finished product rhenium product according to demand.Above-mentioned advantage is specific as follows: prepare theoretical density greater than 99%, thickness can be accomplished 0.4mm, and size can reach the rhenium sheet of 320 * 320mm.
Embodiment
Adopt preparation method of the present invention, prepared 5 batches of rhenium sheets, table 1 is processing step of the present invention and processing parameter, and table 2 is an embodiment of the invention final finished performance perameter table.
High-purity rehenic acid ammonium is crushed to-100～-300 orders, and reduction temperature is 230～350 ℃ for the first time, and product is ground fragmentation-100～-150 sieves, carries out secondary reduction then, and reduction temperature is 800～950 ℃, prepares the high-purity rhenium powder of about 2～6 μ m of granularity.In the high-purity rhenium powder end, add the binding agent of 2% (mass percent), be pressed, make the blank that thickness is 5～15mm with special removable mold.The high-temperature hydrogen sintering oven that blank is put into 2000-2340 ℃ carries out sintering, and obtaining thickness is the sintering blank of 4～12mm.Adopt four-high mill that the sintering blank is carried out cold rolling processing, each deflection is controlled at 8～15%, after each distortion, carries out 1500～1800 ℃ of annealing once.Be rolled repeatedly, anneal, finally making thickness is 0.4mm, is of a size of the square rhenium thin slice of 320 * 320mm.
Table 1 is processing step of the present invention and process parameter table
Table 2 is an embodiment of the invention final finished performance perameter contrast table
| Sequence number | Theoretical density % | Thickness mm | Size mm | |
| The embodiment of the invention | 1 | 99.1 | 0.7 | 310×310 |
| 2 | 99.5 | 0.3 | 180×180 | |
| 3 | 99.2 | 0.8 | 330×330 | |
| 4 | 99.4 | 0.94 | 340×340 | |
| 5 | 99.3 | 0.4 | 210×210 | |
Claims (2)
1. the manufacture method of a difficult-to-form pure rhenium sheet is characterized in that this method comprises following concrete steps:
A, powder process and reduction:
At first with high-purity rehenic acid crystalline ammonium particle through pre-treatment, be crushed to-100～-300 orders; In hydrogen, carry out low-temperature reduction then, control reduction temperature, and reduzate is handled again, grind broken mistake-100～-150 mesh sieves at 230～350 ℃; Then in hydrogen, carry out sufficient secondary reduction, control reduction temperature at 800～950 ℃, obtain oxygen level less than 0.1% and granularity be 2～6 μ m, the pure rhenium powder of purity＞99.95%;
B, pressed compact:
The employing removable mold is pressed, and pressed compact is realized under without any the situation of reactive force separating with pressing mold also can safe transfer; Be aided with the lubricant that adds 1.5～3% (mass percents) in powder simultaneously, making thickness is 5～15mm, and the Poisson's Ratio value is greater than 16 pressed compact;
C, sintering warpage:
Carry out high temperature sintering after pressed compact process dewaxing treatment and the pre-burning under hydrogen shield, sintering temperature is controlled at 2000～2340 ℃, reaches more than 95% of theoretical density until density, and thickness is 4～12mm, the sintering blank that crystallization is even, fine and closely woven;
D, rolling deformation:
What adopt is cold rolling processing at normal temperatures, and strict control pass deformation 8～15%; Adopt every time distortion back in hydrogen, to carry out The high temperature anneal, 1500～1800 ℃ of annealing temperatures, annealing time is 30～120min, make it eliminate work hardening phenomenon and crystallization control is evenly fine and closely woven, then descend a time rolling, circulation is processed like this, thermal treatment is until reaching desired size; Last annealed processing obtains finished product rhenium sheet.
2. the manufacture method of difficult-to-form pure rhenium sheet according to claim 1 is characterized in that lubricant is a kind of in paraffin or the glycide.
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| CNB2007101792629A CN100489131C (en) | 2007-12-12 | 2007-12-12 | Method for manufacturing difficult-to-form pure rhenium sheet |
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| CNB2007101792629A CN100489131C (en) | 2007-12-12 | 2007-12-12 | Method for manufacturing difficult-to-form pure rhenium sheet |
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| CN101177748A true CN101177748A (en) | 2008-05-14 |
| CN100489131C CN100489131C (en) | 2009-05-20 |
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Cited By (14)
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| CN103774020A (en) * | 2014-01-23 | 2014-05-07 | 安泰科技股份有限公司 | Method for preparing molybdenum-rhenium alloy foil |
| CN106077617A (en) * | 2016-08-18 | 2016-11-09 | 中铼新材料有限公司 | A kind of manufacture method of ultra-thin high-purity rhenium paper tinsel |
| CN106270530A (en) * | 2016-08-18 | 2017-01-04 | 中铼新材料有限公司 | A kind of manufacture method of high density pure rhenium test tube |
| CN107052357A (en) * | 2017-04-12 | 2017-08-18 | 湖南元极新材料有限公司 | A kind of preparation method of high-purity rhenium powder |
| CN107838431A (en) * | 2017-11-16 | 2018-03-27 | 重庆材料研究院有限公司 | A kind of spherical rhenium powder, preparation method thereof |
| CN108160995A (en) * | 2017-12-25 | 2018-06-15 | 安泰天龙钨钼科技有限公司 | The preparation method of pure rhenium product |
| CN108213441A (en) * | 2017-12-25 | 2018-06-29 | 安泰天龙钨钼科技有限公司 | A kind of preparation method of pure rhenium pipe |
| CN108296487A (en) * | 2017-12-25 | 2018-07-20 | 安泰天龙钨钼科技有限公司 | A kind of preparation method of pure rhenium plate |
| CN109351985A (en) * | 2018-10-19 | 2019-02-19 | 浙江工业大学 | A kind of method that Hydrothermal Pressure Hydrogen Reduction prepares rhenium metal powder |
| CN109773206A (en) * | 2019-03-29 | 2019-05-21 | 中国科学院金属研究所 | A kind of ultrapure superfine rhenium powder and preparation method thereof |
| CN109794598A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院金属研究所 | A kind of preparation method of ultra-pure rhenium ingot |
| CN113058999A (en) * | 2021-04-06 | 2021-07-02 | 中铼新材料有限公司 | Method for manufacturing ultrathin rhenium foil |
| CN113333771A (en) * | 2021-06-11 | 2021-09-03 | 安泰科技股份有限公司 | Rhenium powder and rhenium product with purity of 6N or above and preparation method thereof |
| CN114535339A (en) * | 2022-01-31 | 2022-05-27 | 北京科技大学 | Processing method of large-size uniform high-purity rhenium plate |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3192011A (en) * | 1963-08-07 | 1965-06-29 | Chase Brass & Copper Co | Process for producing high purity rhenium compounds |
| DE10155237A1 (en) * | 2001-11-09 | 2003-05-22 | Starck H C Gmbh | Process for the production of rhenium |
| CN1175951C (en) * | 2002-07-08 | 2004-11-17 | 株洲硬质合金集团有限公司 | Process for preparing high-purity rhenium powder |
| JP4347783B2 (en) * | 2004-11-04 | 2009-10-21 | 日鉱金属株式会社 | Method for recovering platinum and rhenium from spent catalyst |
-
2007
- 2007-12-12 CN CNB2007101792629A patent/CN100489131C/en active Active
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| CN103774020A (en) * | 2014-01-23 | 2014-05-07 | 安泰科技股份有限公司 | Method for preparing molybdenum-rhenium alloy foil |
| CN106077617A (en) * | 2016-08-18 | 2016-11-09 | 中铼新材料有限公司 | A kind of manufacture method of ultra-thin high-purity rhenium paper tinsel |
| CN106270530A (en) * | 2016-08-18 | 2017-01-04 | 中铼新材料有限公司 | A kind of manufacture method of high density pure rhenium test tube |
| CN106077617B (en) * | 2016-08-18 | 2018-05-04 | 中铼新材料有限公司 | A kind of manufacture method of ultra-thin high-purity rhenium paper tinsel |
| CN107052357A (en) * | 2017-04-12 | 2017-08-18 | 湖南元极新材料有限公司 | A kind of preparation method of high-purity rhenium powder |
| CN107838431A (en) * | 2017-11-16 | 2018-03-27 | 重庆材料研究院有限公司 | A kind of spherical rhenium powder, preparation method thereof |
| CN109794598A (en) * | 2017-11-17 | 2019-05-24 | 中国科学院金属研究所 | A kind of preparation method of ultra-pure rhenium ingot |
| CN108296487A (en) * | 2017-12-25 | 2018-07-20 | 安泰天龙钨钼科技有限公司 | A kind of preparation method of pure rhenium plate |
| CN108213441A (en) * | 2017-12-25 | 2018-06-29 | 安泰天龙钨钼科技有限公司 | A kind of preparation method of pure rhenium pipe |
| CN108160995A (en) * | 2017-12-25 | 2018-06-15 | 安泰天龙钨钼科技有限公司 | The preparation method of pure rhenium product |
| CN108160995B (en) * | 2017-12-25 | 2020-03-06 | 安泰天龙钨钼科技有限公司 | Process for preparing pure rhenium products |
| CN109351985A (en) * | 2018-10-19 | 2019-02-19 | 浙江工业大学 | A kind of method that Hydrothermal Pressure Hydrogen Reduction prepares rhenium metal powder |
| CN109351985B (en) * | 2018-10-19 | 2021-08-10 | 浙江工业大学 | Method for preparing metal rhenium powder by hydrothermal hydrogen reduction |
| CN109773206A (en) * | 2019-03-29 | 2019-05-21 | 中国科学院金属研究所 | A kind of ultrapure superfine rhenium powder and preparation method thereof |
| CN113058999A (en) * | 2021-04-06 | 2021-07-02 | 中铼新材料有限公司 | Method for manufacturing ultrathin rhenium foil |
| CN113058999B (en) * | 2021-04-06 | 2022-05-10 | 中铼新材料有限公司 | Method for manufacturing ultrathin rhenium foil |
| CN113333771A (en) * | 2021-06-11 | 2021-09-03 | 安泰科技股份有限公司 | Rhenium powder and rhenium product with purity of 6N or above and preparation method thereof |
| CN114535339A (en) * | 2022-01-31 | 2022-05-27 | 北京科技大学 | Processing method of large-size uniform high-purity rhenium plate |
| CN114535339B (en) * | 2022-01-31 | 2023-10-10 | 安泰科技股份有限公司 | Processing method of large-size homogenized high-purity rhenium plate |
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